Color printing



Patented 29, 1943 OFFlCE coma ram'rmq Pierre Drewsen and John It. Little,

Sandusky,

Ohio, asslgnor to The Hinde & Dauch Paper m y. 7 Ohio No Drawing.

Sandusky, Ohio, a corporation of Application September 2, 1938, Serial No. 228,212

2 Claims. (Cl. 106-152) I This application is a continuation in part of the co-pending application of Pierre Drewsen and John R. Little, Serial No. 151,684, filed July 2, 1937, for Resinous composition." 'l ne invention to which this particularly relates is a composition of matter useful for bleed-proof coloring, especially of paper and other sheet material, and to methods of applying the same. The present application discloses two related uses, partly disclosed in Serial No. 151,884, of a prolamine-resin composition. One of such uses is as a vehicle for coloring with or without a further protective coat and the other is as a protective coat for a colored surface.

In particular we propose dissolving rosin in aqua ammonia, mixing therewith zein pretreated with aqua ammonia, adding color to the mixture, and using the composition substantially as an ink. This may or may not be followed by over-printing with the same composition, either uncolored, as a transparent protective coating, or carrying transparent colors for composition effects. For pre-treatment of the zein and for dissolution of the rosin we may substitute NaOH or KOH for NHdOH, but prefer the latter be- In Steps 1 and 1s, NaOl-I or x011 may be substituted for NHAOH, or the zein resinate may be made according to Formula B or Formula C.

Formula B 20 lbs. zein (dry weight) I 10 lbs. rosin (dry weight) 1 /2 to 2 lbs. NaOH (or K011i S'rsr 2.Zein resinate The ammonium resinate (Step 1A) 0011113081.

tion may be added to the prepared zein (Step 1)- as soon as all the rosin is dissolved. As soon as the ammonium resinate is added the zein dissolves and the solution -becomes very thick.

cause it is a milder reagent, which can be handied with less care.

The foregoing principles can be applied using compositions having some variation in detailed formula,'lbut those which follow are successful in practice.

Steps 1, 1A and 2 show the fundamental or ground coat, which is the color vehicle. There is no particular time relation between Steps 1 and 1A, that is, they need not be in sequence.

S'rrr l.Prepared zein To 100 pints cold water, add 50 lbs. zein (dry weight), and

4 pints aqua ammonia.

Stir vigorously, keeping the mixture cool enough (below about 100 F.) to prevent agglomerationof the zein.

' Srrr lA.-Ammonium resinate To 3 gals. hot water add simultaneously 6% pints aqua ammonia. and lbs. powdered rosin (dry weight).

Keep heated and stir until dissolved. Heating temperatures are not critical but must not be great enough to drive oil too much ammonia, hence a range below 200 F. is satisfactory; enough ammonia must stay to keep the rosin dissolved.

Make it up to 400 pints with hot water (the zein can no longer agglomerate), mix for about five minutes. This gives a stable liquid which can be kept on hand indefinitely and used as the fundamental composition for further work. The compositions of Steps 1 and 1A may be used in various proportions, the practical limits being from equal quantities of rosin and zein to three times as much zein as rosin.

When color printing is to be done, the color room operator takes a quantity of the foregoing stable mixture, and adds thereto coloring material, also adding hot water and a plasticizer if required. In detail, take from 11 to 18 pints of zein resinate (Step 2) and add thereto the required quantity of aniline dye in 3.5 to 4 pints hot water mixed with 1 pint or more of sulphonated castor oil.

The aniline dye of Step 3 may be any single dye or mixture appropriatefor the color desired. for example, safranine and auramine give a more or less golden. red, according to proportions; blues, greens andso on may be employed. Or a quantity of properly ground dry pigment which per se is not water soluble may be used where a pigment color instead of a dye is desired, for example to give greater opacity or light fastness.

To give a black paper, carbon black is used, and

The function of the sulphonated castor oil is 'stituted for the oxalic.

resinate which is otherwise caused by residual sodium chloride in the dyes. Consequently castor oil may be omitted it pigments are used instead of dyes or if the dyes are free from sodium chloride or other electrolytes. The use of sulphonated castor oil, however, has been found to be beneficial to subsequent printing.

srnr 4 Print the foregoing on a design roll oi the usual type, such for example as that shown in Drewsen Patent No. 2,089,949 of August 17, 1937.

Sup 5 After printing (and after drying the color coat) run the web through another roller, thereby applying the zein coating made according to Formula D, below.

Formula D 16 pints 60% to 95% commercial denatured alcohol 4 pints water Add thereto with rapid mixing 2 to 5 lbs. powdered min and 1 to 3oz. oxalic acid. 7

This mixture is applied by the usual rubber coating roll, and forms a water repellant coating due to the combination of the oxalic acid with the alkali of the preceding coat, where 16 pints water solution of 60% to 95% acetone, or 16 pints 60% to 95% Celloso1ve" i (CaHsOCI-IzCHzOH) Other organic acid of like nature may be sub- Acetic acid will work so far as the zein is concerned but its generally corrosive nature is injurious to the printing equipment. Also, acetic acid does not make the zein solution quite so fluid as does oxalic.

Any of the foregoing coatings, Formula A, B or C, are fairly bleed-proof when applied by themselves, without the protective coat of Formuia' D. That is, without the protective coat no appreciable amount 0! color will come oil. when the colored sample is held under running water. The addition of the protective coating, however, not merely adds to the bleed-proofing oi the color by 'the physical effect 01' a transparent top layer, but also fixes the first coat no color will come oil. on a damp white cloth rubbed over the colored surfalce several times with a pressure of flve pounds or so to the square inch.

Thus it will be seen that we have invented a coloring method which" may be oi. either a moderate or a high quality of resistance to bleeding when wet, and thus adapted selectively either for cheaper or more expensive boxes, particuprinting or coloring of one sort or another is desired, either for ornamentation, for advertising, or for information, "but which must resist smearing when handled, and must not rub oil on the clothes of customers if carried in wet weather.

Other modes of applying the principle of our invention may be employed instead of the one explained, change being made as regards the composition and method herein disclosed, provided the ingredients or steps stated by any of the'following claims or the equivalent of such stated ingredients or steps be employed.

We therefore particularly point, out and distinctly claim as our invention:

1. A coloring liquid comprising aqueous zein a rosinate, aniline dye, and sulphonated castor oil.

'2. A coloring liquid comprising basic zein rosinate, aniline dye, and sulphonatedcastor oil.

' PIERRE DREWSEN. JOHN R. LITTLE, 

